Method for protecting plants against insects and mites with mixed sulfite esters



United States Patent METHOD FOR PROTECTING PLANTS AGAHVST INSECTS ANDMITES WITH D SULFITE ESTERS Rupert A. Covey, Wolcott, Allen E. Smith,Oxford, and Winchester L. Hubbard, Woodbridge, Comm, assignors to UnitedStates Rubber Company, New York, N.Y., a corporation of New Jersey NoDrawing. Original application Aug. 20, 1962, Ser. No. 218,112, nowPatent No. 3,179,684, dated Apr. 20, 1965. Divided and this applicationDec. 21, 1964, Ser. No. 420,098

7 Claims.

This application is a division of our application Serial No. 218,112,filed Aug. 20, 1962, now U.S. Patent 3,179,684, which is acontinuation-in-part of our application Serial No. 131,742, filed Aug.16, 1961, now abandoned.

This invention relates to new chemicals, namely new organic esters ofsulfurous acid, more particularly to mixed sulfite esters of acyclicallrynyl alcohols and saturated aliphatic alcohols or phenols.

The new compounds of the present invention are useful as insecticides,particularly for the control of insects and mites. They may also be usedas plasticizers.

The chemicals of the present invention may be represented by the generalformula in which R is an aliphatic radical, e.g., alkyl, having up to 18carbon atoms, aralkyl, cyanoalkyl, haloalkyl having up to carbon atomsand up to 3 halo radicals or carbalkoxyalkyl radical, or R is anaromatic radical, e.g., aryl (phenyl or naphthyl), alkaryl or haloaryl,and R is an acyclic alkynyl radical. Examples of R are "methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, tert.- butyl, amyl,hexyl, Z-ethylhexyl, octyl, decyl, isodecyl, dodecyl, hexadecyl,octadecyl, benzyl, 2-cnloroethyl, 2- cyanoethyl, Z-carbethoxyethyl,2,2,2-trichloroethyl, 'ychloropropyl, E-chlorobutyl, w-trichloroamyl,phenyl, lnaphthyl, 2-naphthyl, p-tolyl, o-tolyl, isopropylphenyl,tert.-'butylphenyl, tert.-arnyl phenyl, nonylphenyl, and haloaryl having1 to 5 halo radicals, e.g., bromophenyl, 2-chlorophenyl, 2,4dichlorophenyl, trichlorophenyl, pentachlorophenyl. Examples of R areacyclic alkynyl radicals having 3 to carbon atoms, i.e., C I-l radicalswhere n is 3 to 10, e.g., propargyl, 1-(3-butynyl), 2-(3-butynyl),2-(2-methyl-3 -butynyl), I-(Z-heptynyl), 1-( 3-nonynyl).

The preparation of the chemicals of the invention may be carried out byreacting the selected alkynyl alcohol with the separately preparedchlorosulfinate of the selected alcohol or phenol, which may be made byreacting the selected aliphatic or aromatic monohydroxy compound(alcohol or phenol) with thionyl chloride. Such preparation isillustrated by the following reactions with the same symbols R, R as inthe above general formula.

may be used, but is generally unnecessary. The second reaction iscarried out in the presence of an 1101 ac- 3,311,534 Patented Mar. 28,1967 ceptor, such as pyridine, dimethyl aniline or trimethylamine, andin a solvent such as benzene, xylene or solvent naphtha. The reactiontemperature is generally between 10 C. and 50 C., preferably near 0 C.

Examples of the sulfite diesters of the present invention are:

Propargyl hexyl sulfite Propargyl sec.-octyl sulfite Propargyl isodecylsulfite Propargyl tridecyl sulfite Propargyl hexadecyl sulfite Propargylbenzyl sulfite Propargyl 2-chloroethyl sulfite Propargyl Z-cyanoethylsulfite Propargyl Z-carbethoxyethyl sulfite Propargyl phenyl sulfitePropargyl o-tolyl sulfite Propargyl p-tert.-butylphenyl sulfitePropargyl 1-naphthyl sulfite Propargyl nonylphenyl sulfite Propargylo-chlorophenyl sulfite 2- S-butynyl) decyl sulfite 2-(3-butynyl)hexadecyl sulfite 2-(3-butynyl) m-tolyl sulfite l-(Z-butynyl) dodecylsulfite 1-(2-butynyl) p-tcrt.-amylphenyl sulfite 1-(3-hexynyl) octadecylsulfite 1-(3-hexynyl) o-tert.-butylphenyl sulfite Example 1 illustratesthe preparation of the compounds of the present invention.

EXAMPLE I Preparation of propargyl tridecyl sulfite Tridecyl alcohol g.,0.5 mole) was cooled to 05 C. Thionyl chloride (45.4 ml., 74.4 g., 0.625mole) was added during one hour keeping the reaction temperature below10 C. The mixture was allowed to Warm to room temperature and stand for15 hours. The mixture was warmed to 50 C. (0.5 mm.) to remove unreactedthionyl chloride. The tridecyl chlorosulfinate residue was anamber-colored oil, yield 141.0 g. (99.8%). The product was nearlyodorless and relatively stable when stored in a refrigerator.

Propargyl alcohol (3.2 ml., 3.1 g., 0.055 mole) 4.1 ml. (4.0 g., 0.05mole) pyridine and 60 ml. xylene were cornbined and the solution cooledto 0-5 C. Tridecyl chlorosulfinate (14.2 g., 0.05 mole) was addeddropwise during 0.5 hr. maintaining the reaction temperature below 8 C.The mixture was stirred for one hour and was washed twice with 25 ml.portions of water. The mixture was then stirred for 1.5 hrs. with 2NNaOH. The xylene solution was washed several times with saturated saltsolution until the washings Were neutral to pH paper. The xylene wasremoved under reduced pressure and the residue distilled, B.P. 122-136"C. (0.1 mm.). Yield 11.4 g. (71%) colorless oil, 11 1.4596.

Analysis.-Calculated for C H O S: C, 63.53%; H, 10.00%; S, 10.60%.Found: C, 64.27%, 64.13%; H, 10.08%, 10.05%; S, 10.39%, 9.34%.

Sulfur analyses of other chemicals of the present invention were:

2-(3-butynyl) hexadecyl sulfite.Calculated S, 8.94%. Found: 8.34%.

Propargyl decyl sulfite. Calculated S, 12.31%. Found: 12.22%.

1-(2-butynyl) tridecyl sulfite-Calculated S, 10.13%. Found: 10.14%.

Propargyl o-tolyl sulfite-Calculated S, 15.26%. Found: 15.25%.

Propargyl hexadecyl sulfite.-Calculated S, 9.31%. Found: 8.63%.

EXAMPLE II This example illustrates the insecticidal. activity of thechemicals of the present invention in tests against the larvae of Aedesaegypti (L.) mosquitoes. Fourth instar larvae were used. These larvaenormally reach this stage in 5 days 80 F. after hatching.

To mg. of the chemical to be tested was added 1 ml. of acetone and 100ml. of water to give a concentration of 100 parts per million (ppm), anda portion was also diluted to 10 ppm.

Twenty-five ml. aliquots, replicated once, of the chemical to be testedat concentrations of 100 ppm. and 10 p.p.m. and of checks without thechemical and of plain water checks were placed in test tubes and from 5to larvae were added. The tubes were held at 70 F. in darkness for 72hours. At the end of this period the live and dead larvae were countedand the percent mortality calculated. All the larvae were alive in thechecks (0% mortality). The percent mortality of the larvae treated withthe chemical of the present invention is shown in the following table:

EXAMPLE III This example illustrates the edectiveness of the chemicalsof the present invention for controlling mites.

Pinto beans in the two-leaf state and grown in 4 baskets undergreenhouse conditions at 70 F.75F. were used. Three plants for a totalof six leaves were in each basket for each test. The tests on thechemicals and checks were replicated once. Aqueous suspensions of thechemicals were prepared by adding to 0.2 gram of the chemical one drop(0.03 gram) of a commercial surface-active dispersing agent(isooctylphenyl polyethoxy ethanol) and 1 ml. of acetone, washing into200 ml. of water, agitating to form a dispersion and diluting with waterto the desired concentrations of 1000 ppm. and 200 p.p.m.

The plants were sprayed with the dispersions of the chemicals at thevarious concentrations and the check plants were sprayed with aqueoussolutions containing surface-active agent and acetone without thechemicals. The sprayings thoroughly wet the upper surface of the leaves.The plants were returned to the greenhouse. The following day (20-24hours later), rings of an adhesive preparation non-toxic to theorganisms under test, such as is used on fly papers and for ringingtrees, were placed around the borders of the upper surfaces of theleaves to restrict the mites to the upper leaf surfaces. Mites weretransferred to the thus treated leaves by placing bean leaflets heavilyinfested with two spotted adult mites. Tetranyclzus tet'arius L. withinthe border of the adhesive preparation on the leaves of the plants undertest. A count of the number of mites transferred were made the same day.The counts ranged from to 300 mites on the six leaves. The plants werekept in the greenhouse for another four days. A final count of thenumber of living mites remaining on the leaves was then made. Thepresent control is found by using the formula:

final count living mites percent control 100(1 Original count .51following table (the check treatments without the chemicals had about20% mortality):

This example also illustrates the effectiveness of the chemicals of thepresent invention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4" baskets undergreenhouse conditions at 70 F.*75F. were used. Two plants for a total offour leaves were in each basket for each test. These tests on thechemicals were replicated once.

The untreated leaves were ringed with adhesive and 4050 mites weretransferred to each leaf similarly to Example III.

The plants were then sprayed to thoroughly wet the upper surface of theleaves with aqueous solutions of the chemicals at concentrations of ppm.and 50 ppm. prepared as in Example 111.

The plants were allowed to dry and a count of the mites was made. Theplants were kept in the greenhouse for three days. A final count of theliving mites remaining on the leaves was then made. The percent controlis found by the formula used in Example III.

The control of mites by the chemicals of the present invention is shownin the following table:

The chemicals of the present invention may be applied in various mannersfor the control of insects. They may be applied to loci to be protectedagainst insects as dusts when admixed with or adsorbed on powdered solidcarriers, such as the various mineral silicates, e.g., mica, talc,pyrophillite and clays, or as liquids or sprays when in a liquidcarrier, as in soiution in a suitable solvent, such as acetone, benzeneor kerosene, or dispersed in a suitable non-solvent medium, for example,water. In protecting plants (the term including plant parts) which aresubject to attack by insects, the chemicals of the present invention arepreferably applied as aqueous emulsions containing a surface-activedispersing agent, which may be an anionic, non-ionic or cationicsurface-active agent. Such surface-active agents are well known andreference is made to US. Patent No. 2,547,724, columns 3 and 4 fordetailed examples of the same. The chemicals of the invention may bemixed with such surface-active dispersing agents, with or without anorganic solvent as insecticidal concentrates for subsequent addition ofwater to make aqueous suspensions of the chemicals of the desiredconcentration. The chemicals of the invention may be admixed withpowdered solid carriers, such as mineral silicates together with asurface-active dispersing agent so that a wettable powder may beobtained, which may be applied directly to loci to be protected againstinsects, or which may be shaken up with water to form a suspension ofthe chemical (and powdered solid carrier) in water for application inthat form. The chemicals of the present invention may be applied to locito be protected against insects by the aerosol method. Solutions for theaerosol treatment may be prepared by dissolving the chemical directly inthe aerosol carrier which is liquid under pressure but which is a gas atordinary temperature (e.g., 20 C.) and atmospheric pressure, or theaerosol solution may be prepared by first dissolving the chemical in aless volatile solvent and then admixing such solution with the highlyvolatile liquid aerosol carrier. The chemicals may be used admixed withcarriers that are active of themselves, for example, other insecticides,fungicides or bactericides.

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

1. The method of protecting plants against attack by insects and miteswhich comprises applying to the plants a compound having the formula inwhich R is an alkyl having up to 18 carbon atoms, benzyl, cyanoethyl,carbethoxyethyl, chloroalkyl having up to 5 carbon atoms and up to 3chloro radicals, phenyl, naphthyl, phenyl and naphthyl havingsubstituents consisting of up to 5 halo radicals selected from the classconsisting of bromo and chloro, or mono-substituted phenyl and naphthylhaving as the substituent an alkyl having up to 9 carbon atoms, and R isacyclic alkynyl of the formula C H -in which n is 3 to 10.

2. A method for protecting plants against attack by insects and miteswhich comprises applying to the plants propargyl hexyl sulfite.

3. A method for protecting plants against attack by insects and miteswhich comprises applying to the plants propargyl decyl sulfite.

4. The method of protecting plants against attack by insects and miteswhich comprises applying to the plants propargyl tridecyl sulfite.

5. The method of protecting plants against attack by insects and miteswhich comprises applying to the plants I-(Z-butynyl) tridecyl sulfite.

6. The method of protecting plants against attack by insects and miteswhich comprises applying to the plants 2-(3-butynyl) hexadecyl sulfite.

7. The method of protecting plants against attack by insects and miteswhich comprises applying to the plants propargyl o-tolyl sulfite.

References Cited by the Examiner UNITED STATES PATENTS 2,465,391 3/1949Myles 260456 2,529,493 11/1950 Harris et al 260456 X 2,802,727 8/1957Harris et a1. 260456 X 2,820,808 1/1958 Harris et al. 260456 2,867,5641/1959 Richter 167-30 2,885,278 5/1959 Brack 260456 X 2,905,587 9/1959Dowling 16730 JULIAN S. LEVITT, Primary Examiner. GEORGE A. MENTIS,Assistant Examiner.

1. THE METHOD OF PROTECTING PLANTS AGAINST ATTACK BY INSECTS AND MITESWHICH COMPRISES APPLYING TO THE PLANTS A COMPOUND HAVING THE FORMULA